PL155144B1 - Antimycotic agent - Google Patents

Abstract

The invention provides a fungicidal composition comprising at least one systemic, contact and/or soil fungicide and at least one acrylic acid morpholide derivative of the general formula <CHEM> in which R1 represents a hydrogen, chlorine or bromine atom, a trifluoromethyl, trifluoromethoxy, C3-C7 alkyl, C3-C5 alkoxy, C3-C6 alkenyl, HClFC-CF2O-, HClC=CClO-, cyclohexyl, cyclopentenyl, cyclohexenyl, phenyl, 4-chlorophenyl, 4-ethylphenyl, 4-chlorobenzyl or 4-chlorophenylthio group or a phenoxy group optionally substituted by one or more substituents selected from fluorine and chlorine atoms and methyl and ethoxycarbonyl groups and R2 represents a hydrogen atom, or R1 represents a hydrogen atom and R2 represents a 3-phenoxy group.

Description

THE REPUBLIC OF POLAND

PATENT DESCRIPTION

Additional patent to patent no -

Reported: 88 01 29 / P. 270 365 /

Priority 87 01 30 Federalru 155 144

Int. Cl. 8 A01N 59/26 A01N 43/84

PATENT OFFICE OF THE RP

Application announced: 88 09 29 Patent specification published: 1992 01 31

Inventor j

The holder of the patent: Shell Agrar GmbH and Co., KG.,

Ingelheim on the Rhine / Federal Republic of Germany /

FUNGICIDE

The present invention relates to a fungicide which is a combination of fungicidal substances such as acrylic acid morpholide in combination with certain systemic fungicides.

Many different compounds are known and are used as systemic fungicides. Examples of such compounds that are commercially available can be found, for example, in "The Pesticids Manual", Eighth Edition, 1987, published by Charles R. Worthing and S. Barrie Walker, published by The British Crop Protection Council. It is also known that some acrylic acid morpholide derivatives are effective in controlling phytopathogenic fungi. Examples of such compounds are given in European Patent Applications Nos. 120321 and 219756.

It has now been found that the fungicidal activity of some of these acrylic acid morpholides can be improved to a surprising degree when used in combination with certain systemic fungicides.

The invention relates to a fungicide containing a systemic fungicide such as phosphoric acid or aluminum tris / ethylphosphonate and a morpholide derivative of acrylic acid of the general formula shown in the figure, in which R represents a chlorine atom or a phenyl group and optionally known auxiliaries.

The ratio of the vegan acrylic morpholide derivative to the systemic fungicide is 1: 160-50: 1, preferably 1:20-10: 1.

Examples for the preparation of morpholide derivatives of acrylic acid of the general formula shown in the figure are given in European Patent Applications Nos. 120321 and 219756. 155 144 2 155 144

Examples of systemic fungicides which are suitable for use are given below: Systemic fungicides 1. Benalaxyl: N-phenylacetyl-N-2,6-xylyl-0, L-methyl alaninate, 2. Cymoxanil: 1- / 2-cyano-2- methoxyiminoacetyl) -3-ethylurea, 3. Cyprofuran; / - / - o £ - / N- / 3-chlorophenyl / cyclopropane carboxaaldo / - &quot; Jf - butyrolactone, 4. Matalaxyl: N- (2-methoxyacetyl) -N- / 2,6-xylyl / -D, L- Betyl alanoate, 5. Ofurace: / ± / -oC-2-chloro-N-2,6-xylloacetamido-Ύ -butyrolactone, 6. Oxadixyl: 2-methoxy-N- / 2-oxo-1,3-oxazolidine- 3-yl / octo-2 ', 6'-xylidide, 7. Phosetyl-aluainium: Tris / atylphosphonate / aluminum 8 · Phosphoric acid and its salts · Among the above-mentioned systemic fungicides, cymoxanil, foaethyl-aluminum, phosphoric acid and disodium phosphite. It is believed that the better effect of the agents according to the invention is due to synergism or resistance to degradation. A further advantage of the agents according to the invention is the broader spectrum of activity. tobacco, hops, pumpkin, squashes and other vegetables, rubber trees, citrus fruits, avocados, pineapples, cocoa trees, roses, cloves and other ornamental plants.

Combinations of compounds of the general formula shown in the figure and compounds of the group of systemic fungicides sg are also particularly suitable for controlling fungal diseases of the grapevine when the plant is infected (curative effect).

The amounts of active ingredients used in the compositions according to the invention depend on the application rate when used alone and on the ratio of one product to another and the degree of synergism. The action of the agent is also important. The relative ratios between the compounds of the general formula shown in the figure and those of the group of systemic fungicides may in extreme cases be from 1: 160 to 50: 1 parts by weight of active ingredient, but preferably from 1:20 to 10: 1.

Detailed information on the amounts of ingredients used is given below.

The compounds of the general formula shown in the figure are used in concentrations from 25 - 1000 ppm, preferably from 100 to 500 ppm, while the amounts of compounds to be combined with them should be as follows (all numbers are given in ppm): tris / ethylphosphonate / aluminum 100 - 2500 phosphoric acid and its salts 100-4000 / 600-2000 / The agent according to the invention may also contain a carrier, the active ingredients being present in it in a total amount of 0.5 to 95% by weight.

A carrier in the composition of the invention is any substance with which the active ingredient is combined to facilitate application to the site to be treated, which may be, for example, plants, seeds or soil, or to facilitate storage, transport or handling. The carrier can be solid or liquid, including a substance which is usually a gas but can be compressed to form a liquid, and any carriers conventionally used in formulating fungicides can be used. the compositions according to the invention may be formulated as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, dissolving powders, granules, suspending or emulsifying concentrates or as aerosols. Solutions and powders enclosed in polymeric capsules are also suitable, such as natural or synthetic substances or carriers impregnated with the active ingredient. These preparations are prepared in the usual manner, such as by mixing the active ingredient with liquid solvents and / or solid carriers with the addition of surfactants, i.e. emulsifiers and / or dispersants, stabilizers, wetting agents, heavy agents, dyes, and perfumes. . The method of obtaining fungicides consists in combining the active ingredients with at least one carrier.

If water is used as a solvent or diluent. organic solvents can also be used as auxiliary solvents or anti-freeze additives for water * Suitable organic solvents include aromatic solvents such as benzene, xylene, toluene, alkylbenzenes, alkyl naphthalenes, and chlorinated aromatic solvents; chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene, trichloroethane, methylene chloride, chloroform, carbon tetrachloride and polychloroethane; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oils, paraffins and kerosene, however particularly suitable are polar solutions, i.e. alcohols such as isopropanol, butanol, glycols, benzyl alcohol, furfuryl alcohols and cyclohexanol as well as their ethers and esters ; methyl ethyl ketones, methyl isobutyl ketone, cyclohexanone, T-butyrolactone and dimethylformamide, dimethylsulfoxide and N-aethylpyrrolidone. Mixtures of different liquids are often suitable.

Suitable solid supports include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earth; magnesium silicates for example talcs, magnesium aluminum silicates for example attapulgites and vermiculites, aluminum silicates for example keolinite, montmorillonites and mica; calcium carbonate, calcium sulfate, ammonium sulfate, synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates, elements for example carbon and sulfur, natural and synthetic resins, for example coumarone resins, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenbles, bitumen, waxes and solid fertilizers, for example superphosphates. In particular, suitable solid carriers for powders or dusts include naturally occurring rock fluff, montmorillonite, diatomaceous earth or diatomite and synthetic minerals such as micro-dispersed silicic acid or alumina, suitable granular carriers include crushed and graded natural rocks such as limestone, marble. , pumice stone, sepiolite and dolomite and synthetic granules made of organic and inorganic flours. In addition, granules can be made from organic substances such as sawdust, coconut shell flour, corn cob fibers and dried tobacco stalks. Agents for agricultural use are often formulated and shipped as concentrates that are substantially diluted at the consumer prior to use. The presence of small amounts of a carrier which is a surfactant facilitates the dilution process. Thus, it is preferred that at least one carrier in the composition of the invention is a surfactant. For example, the agent may contain at least two carriers, at least one of which is a surfactant. The surfactant can be an emulsifying agent, dispersing agent or wetting agent, and it can be non-ionic or ionic. Examples of suitable surfactants include sodium or calcium salts of polyacrylic acids and lignosulfonic acids, condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in an ethylene oxide and / or propylene oxide molecule; fatty acid esters of glycerin, sorbitol, sucrose or pentaerythritol; condensation products thereof with ethylene oxide and / or propylene oxide; condensation products of fatty alcohol or alkylphenols, for example p-octylphenol or p-ocrylcresol, with ethylene oxide and / or propylene oxide; sulfates or sulfonates of these condensation products, alkali metal or alkaline earth metal salts, preferably sodium salts of sulfuric or sulfonic acid esters containing at least 10 carbon atoms in the molecule, e.g. sodium lauryl sulfate, secondary sodium alkyl sulfates, sodium sulfonated towel oil and alkyl arylsulfonates sodium such as dodecylbenzene sulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide. In particular the following substances can be used as emulsifying and / or wetting agents; non-ionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, ethoxylated towel oil, and non-ionic emulsifiers such as acidic and neutral alkylsulfonates, alkylsulfates and arylsulfonates, and cellulosic derivatives and lignosulfite derivatives can be used. Heavy agents such as carboxymethyl alcohol, natural water-soluble polymers such as gum arabic, and synthetic polymers in powder, granule, or latex form such as polyvinyl alcohol or polyvinyl acetate can be included in the formulations.

The formulations may contain dyes in the form of inorganic pigments such as iron oxide, titanium oxide or Prussian blue, or organic dyes such as alizarin, azo dyes, metallic phthalocyanines or triphenylmethane dyes. They may also contain fragrances, such as natural essential oils. Depending on the type, the preparations preferably contain from 5% to 85% by weight of active ingredient, solid preparations preferably containing 20-80% by weight of active ingredient, preparations in which the active ingredient is in solution contain 10-15% by weight of active ingredient. and formulations in which the active ingredient is in suspension contain 10-60% by weight of the active ingredient.

Wettable powders usually contain 25, 50 or 75% by weight of active ingredient and usually contain, in addition to solid inert carrier, 3 - 10% by weight of dispersant and, if necessary, 0-10% by weight of stabilizer (s) and / or other additives such as wetting agents or agents. increasing the stickiness. Dusts are usually formulated as dust concentrates with a composition similar to a wettable powder but without dispersant and are diluted in the field with a further amount of solid carrier to give a composition usually containing 0.5-10% by weight of active ingredient. The granules are typically produced in sizes from 10 to 100 BS mesh (1.676-0.152 mm) and may be made by agglomeration or impregnation. Typically the granules will contain 0.5-75% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, surfactants, release retarding modifiers and detergents. So-called "liquid powders" I consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to the solvent and if necessary a co-solvent, 10 - 50% w / v active ingredient, 2 - 20% w / v. emulsifiers and 0 - 20% w / v. other additives such as stabilizers, wetting agents and corrosion inhibitors. The suspension concentrates are usually formulated to give a stable non-sedimentation product and usually contain 10 - 75% by weight of active ingredient, 0.5 - 15% by weight of dispersants, 0.1 - 10% by weight of suspending agents, such as protective colloids and thixotropic agents. 0-10% by weight of other additives such as anti-foaming agents, corrosion inhibitors, stabilizers, wetting agents and tackifiers, and water or an organic liquid in which the active ingredient is substantially insoluble, some organic solids or inorganic salts dissolved in preparation to help prevent sedimentation or as a water antifreeze.

Aqueous dispersions and emulsions, for example obtained by diluting a wettable powder or a concentrate with water, also fall within the scope of the invention. These emulsions may be of the water-in-oil or oil-in-water type and may have a consistency similar to that of mayonnaise. The compositions according to the invention may be in the form of ready-made preparations, i.e. in which the constituent substances are already combined, but may also be provided as separate components for mixing in a tank immediately before use. The concentrates according to the invention are usually mixed with water to obtain the desired active ingredient concentration. The compositions according to the invention may be combined with other ingredients, for example other compounds having herbicidal, insecticidal or fungicidal properties. It is also possible to mix them with nematicides, bird repellants, plant nutrients or soil enrichment ingredients. Of particular interest in increasing the duration of the protective action of active compounds is the use of a carrier which will cause a slow release of the compounds with a fungicidal action to the environment of the plants to be protected. Such sustained active ingredient release agents may, for example, be incorporated into the soil adjacent to the roots of the grapevine plants or may contain an adhesion promoter enabling them to be applied directly to the stems of the grapevines. The compositions according to the invention are applied in the normal way, for example by pouring, spraying, fogging, dusting or scattering. Application rates may vary depending on the weather conditions or the condition of the crops, and may be applied before or after contamination. This is very important when in practice the point at which the infection has occurred cannot be recognized immediately. The duration of protection is usually dependent on the single compound selected and also on many external factors such as climate, the impact of which is usually mitigated by the use of appropriate preparations.

The use of an agent according to the invention consists in controlling the fungi at the site of their occurrence by treating the site, which may be, for example, plants that are attacked or susceptible to fungal attack, the seeds of such plants or the environment in which such plants grow or will grow, with such agent.

The invention is illustrated by the following examples.

Example 1 Emulsifiable concentrate agent: 22.3 wt.% 3.0 wt.% Phosphoric acid β - (4-chlorophanyl) - β - (3,4-dimethoxyphanyl) acrylic acid morpholide sec-butylamine 9.7 % by weight emulsifier / sodium alkylbansenesulfonate / 15% by weight solvent / cyclohexanone / 50% by weight

Phosphoric acid is dissolved in the solvent and then acrylic acid morpholide is added. A clear dark yellow solution is obtained. The solution turns clear on addition of sec-butylamine and emulsifier.

Example II. wettable powder agent fosetyl-aluminum 50% by weight β - / 4-chlorophenyl / -β - / 3,4-dimethoxy-phenyl / acrylic acid morpholide 10% by weight wetting agent / alkyl naphthalene sulphonate / 2% by weight dispersant / lignosulfonate (8% by weight carrier / kaolin) 30% by weight

All the solids are mixed together and ground in an anchor disk mill until particles are about 5-10 µm in size.

Example III. Wettable powder agent disodium phosphite 50% by weight - (4-chlorophenyl) - - / 3,4-dimatoxyphenyl / acrylic acid 5% by weight 2% by weight 10% by weight 8% by weight 25% by weight sodium diisooctylsulfosuccinate / agent wetting agent / sodium sulfate / dispersing agent / lignosulfonate / dispersing agent / kaolin / carrier / N82HPO3 is obtained by neutralizing H2PO3 with NaOH in aqueous solution followed by spray drying. The ingredients are thoroughly mixed and ground in a cat disk mill. The emulsifiable concentrate is 20% by weight 5% by weight 15% by weight

Example IV. Agent in the form of concentrate phosphoric acid β - / 4-biphenyl acid morpholide / - β - / 3,4-dimethoxyphenyl / acrylic emulsifier / ethoxylated triglyceride / solvent / dimethyl glycol diethylene ether / 60% by weight

Phosphoric acid is dissolved in the solvent and then acrylic acid morpholide and emulsifier are added. A clear solution is obtained.

Claims (1)

6 155 144 EXAMPLE 5 The agent of Example 1 is biologically tested in a greenhouse in comparison with a 10% concentrate for emulsifying β - (4-chlorophenyl) -β - / 3,4-dimethoxyphenyl / acrylic acid / and phosphoric acid morpholide . Test plants: grapevines in the third leaf stage / in the greenhouse /. Infection: plasmopara viticola Application: 2 days after infection The concentration range was selected, which enabled observation of the increased effect. r &quot; ------------ and Active substance gam me · &gt; aa · »« ai 4 »as · aa« w a ·. Γ, phosphoric acid 100 ·· «········· combination of both substances Effect in% of dose in ppm: 1 100 1 1 • 747 and 50 Γ and 378 25 1 51 T 1“ * f 1 58 1 1 1 30 I 1 1 1 6, 1 (8 1 1 81 1 70 1 43 i _____- - i- 188 O -ji HI &quot; i I “l I Example 6 Action against plasmopara viticola The active substance i 'and fosetyl were tested separately and in combination in the same way as described in Example V. Dose in ppm to obtain an effect: Active substance 1 50% 1 80% i 'I 100 1 100 Fosetyl I 1000 1 1000 i' + fosetyl 1 25 1 100 1 185 1 747 100ppm Compound i 'had only 50% effect and much more than 1000ppm was required to achieve the same effect with fosetyl. 50% effect was achieved by combining 25ppm i' and 188ppm fosetyl. 100ppm I * and 747ppm fosetyl the effect was 80% EXAMPLE 7 Action against Plasmopara viticola The active compounds β - (4-chlorophenyl) - β - (3,4-dimethoxyphenyl) acrylate / 1V and Al-fosetyl were tested individually and in combination. beam concentration 1 efficiency 1 I 'l 100 ppm 1 1 58.1% Al-fosetyl 750 ppm 1 a 8.8% I 1000 ppm 1 8.1% i' + i 100 ppm 1 Al-fosetyl 750 ppm 1 1 84.4 % Γ + | Al-Fosetyl and 100 ppm 1000 ppm 1 t 86.9% Claims 1. A fungicide containing an active ingredient and optionally known auxiliaries, characterized by containing a systemic fungicide such as phosphoric acid or aluminum tris / ethylphosphonate and acrylic acid morpholide with the general formula